Emission Spectroscopy Based upon Plasma, Arc, and Spark Atomization

Arc
Higher Temperature Lower interelement interference Single set of excitation conditions can excite multiple elements Permit low detection limits for refractory complexes Larger linear range Can directly measure hard to measure samples

Flame
Simpler, less expensive instrumentation Lower operating costs Greater reproducibility

Emission Spectroscopies Cont.

Plasma (def.) Electrically conducting gaseous mixture containing significant concentrations of cations and electrons ICP and DCP

Inductively Coupled Plasma

Inductively coupled means that the plasma is generated due to differences in the magnetic field and currents Temp. very hot (40008000K) Good & bad

Direct Current Plasma (DCP)

Plasma forms by bringing graphite and W electrodes in contact with one another Temp @ core 10,000K in viewing region 5000K

ICP DCP Comparison

DCP is an order of magnitude less sensitive than ICP Similar reproducibilities DCP requires less Ar

Auxillary power less expensive in DCP Graphite electrode must be replaced every couple of hours

Comparison of Plasma to Flame Emission Sources

Plasma sources offer significantly better quantitative data than do other flame emission sources - High stability - Low noise - Low background - Freedom from interferences

Comparison between Atomic Absorption & Emission Techniques

AAS AES

Instruments

Requires HC lamp for each element No high quality MC required

Flame/ sample is source Requires high quality MC

Operator Skill Bkgd.Correction Prec. & Accuracy

Interferences

Detection limit

Comparison between Atomic Absorption & Emission Techniques

AAS AES

Instruments

Requires HC lamp for each element No high quality MC required

Lower skill

Flame/ sample is source Requires high quality MC

Higher skill

Operator Skill Bkgd.Correction Prec. & Accuracy

Interferences

Detection limit

Comparison between Atomic Absorption & Emission Techniques

AAS AES

Instruments

Requires HC lamp for each element No high quality MC required

Lower skill

Flame/ sample is source Requires high quality MC

Higher skill Easier to do

Operator Skill Prec. & Accuracy

Bkgd.Correction Harder to do

Interferences

Detection limit

Comparison between Atomic Absorption & Emission Techniques

AAS AES

Instruments

Requires HC lamp for each element No high quality MC required

Lower skill Unskilled better Same for skilled

Flame/ sample is source Requires high quality MC

Higher skill Easier to do Unskilled worse

Operator Skill Prec. & Accuracy

Bkgd.Correction Harder to do

Interferences Detection limit

Comparison between Atomic Absorption & Emission Techniques

AAS AES

Instruments

Requires HC lamp for each element No high quality MC required

Lower skill Unskilled better Same for skilled

Flame/ sample is source Requires high quality MC

Higher skill Easier to do Unskilled worse

Operator Skill Prec. & Accuracy

Bkgd.Correction Harder to do

Interferences

Spectral interferences corrected Chemical interferences in AES on AE (flame) bad, plasma eliminated

Detection limit

Comparison between Atomic Absorption & Emission Techniques

AAS AES

Instruments

Requires HC lamp for each element No high quality MC required

Lower skill Unskilled better Same for skilled

Flame/ sample is source Requires high quality MC

Higher skill Easier to do Unskilled worse

Operator Skill Prec. & Accuracy

Bkgd.Correction Harder to do

Interferences

Spectral interferences corrected Chemical interferences in AES on AE (flame) bad, plasma eliminated Plasma comparable to flame for some metals, other metals plasma better

Detection limit Flame some metals better on AA than AES

Comparison of Metal Spectroscopic Techniques

Performance Flame Criteria AA Dynamic range Qualitative analysis Elemental range limited Electrothermal Flame Sampling AES limited wide DCP wide ICP Wide

Trace analysis

Comparison of Metal Spectroscopic Techniques

Performance Flame Criteria AA Dynamic range Qualitative analysis Elemental range limited poor Electrothermal Flame Sampling AES limited poor wide DCP wide ICP Wide

excellent excellent excellent

Trace analysis

Comparison of Metal Spectroscopic Techniques

Performance Flame Criteria AA Dynamic range Qualitative analysis Elemental range limited poor Electrothermal Flame Sampling AES limited poor wide DCP wide ICP Wide

excellent excellent excellent excellent excellent excellent

excellent excellent

Trace analysis

Comparison of Metal Spectroscopic Techniques

Performance Flame Criteria AA Dynamic range Qualitative analysis Elemental range limited poor Electrothermal Flame Sampling AES limited poor wide DCP wide ICP Wide

excellent excellent excellent excellent excellent excellent

excellent excellent

Trace analysis

excellent excellent

excellent excellent excellent

Comparison of Metal Spectroscopic Techniques

Performance Flame Criteria AA Dynamic range Qualitative analysis Elemental range limited poor Electrothermal Flame Sampling AES limited poor wide DCP wide ICP Wide

excellent excellent excellent excellent excellent excellent

excellent excellent

Trace analysis

excellent excellent

excellent excellent excellent

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Matrix interfernces Spectral Interferences Precision & Accuracy Costs high Electrothermal Flame Sampling AES high high DCP low ICP low

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Matrix interfernces high Electrothermal Flame Sampling AES high low high low DCP low ICP low

Spectral low Interferences Precision & Accuracy Costs

moderate high

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Matrix interfernces high Electrothermal Flame Sampling AES high low high low Worse for unskilled same skilled DCP low ICP low

Spectral low Interferences Precision & Accuracy Better for unskilled Same skilled

moderate high

Costs

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Matrix interfernces high Electrothermal Flame Sampling AES high low high low Worse for unskilled same skilled $$$ $ $$$ $$$$ DCP low ICP low

Spectral low Interferences Precision & Accuracy Better for unskilled Same skilled $$

moderate high

Costs

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Costs Instrumentat low ion Maintenance Sample Preparation Operator skill low low moderate high Electrothermal Flame Sampling AES DCP ICP

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Costs Instrumentat low ion Maintenance low Sample Preparation Operator skill low low low low moderate high moderate high Electrothermal Flame Sampling AES DCP ICP

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Costs Instrumentat low ion Maintenance low Sample Preparation Operator skill low low low low low moderate high moderate high moderate moderate Electrothermal Flame Sampling AES DCP ICP

moderate moderate

Comparison of Metal Spectroscopic Techniques continued

Performance Flame Criteria AA Costs Instrumentat low ion Maintenance low Sample Preparation Operator skill low low low low low higher moderate high moderate high moderate moderate higher higher Electrothermal Flame Sampling AES DCP ICP

moderate moderate lower higher